Collective intermolecular Coulombic decay beyond Coulomb

Intermolecular Coulombic decay (ICD) is a widely spread phenomenon in nature and the laboratory in which the excess energy of a donor is utilized to ionize a nearby acceptor. If the excess energy is insufficiently large to enable ICD, two (or more) donors can collectively transfer their combined excess energy to ionize the acceptor. Experiments show that this collective ICD is, surprisingly, operative in gases. Recently, it has been demonstrated that standard ICD can take place efficiently at large distances between the donors and acceptors due to retardation. Here, we derive the theory of collective ICD including retardation. Quantum electrodynamics perturbation theory is used, and it is shown that the theory can be substantially simplified and the process made more amenable to interpretation by introducing two-body interaction potentials that include retardation. Explicit formulas for the rate of collective ICD are derived and interpreted by expressing the rate in terms of measurable quantities and geometric factors. It is demonstrated that the change in the permanent dipole moments of the species upon excitation is a relevant ingredient in collective ICD.